Reactive dyestuffs containing a fiber-reactive alkylsulphonylpyrimidyl group

ABSTRACT

wherein R is hydrogen or a lower alkyl radical of 1 to 5 carbon atoms; A is a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, triazine, quinoline, phthalazine, cinnoline, phenazine, or phenanthridine radical which contains at least one lower alkyl sulfonyl, phenyl sulfonyl, benzyl sulfonyl, naphthyl sulfonyl, benzthiazolyl sulfonyl, thiazolyl sulfonyl, thiadiazolyl sulfonyl, oxazolyl sulfonyl, benzimidazolyl sulfonyl, or pyrimidyl sulfonyl, said sulfonyl radical containing no substituents or substituents selected from the class consisting of the bromine, chlorine, hydroxyl, nitro, cyano, sulfo, carboxyl, carboxy lower alkyl, lower carboalkyl, lower carboalkoxy, lower alkoxy, lower alkyl, lower alkyl sulfonyl amino and acetyl amino radical, said reactive sulfonyl substituent being linked to a carbon atom of the heterocyclic moiety A; and m represents a number from 0.5 to 8. The dyeings which can be obtained with the new dyestuffs are characterized by good to very good fastness properties, especially by excellent fastness to wet processing.   WHEREIN F is the radical of an organic dyestuff; X is -CH CH-,   Reactive dyestuffs particularly useful in the dyeing of textile materials containing hydroxyl groups or nitrogen, such as natural and regenerated cellulose, wool, silk, synthetic polyamides, and synthetic polyurethanes, are prepared and have the formula:

United States Patent 1191 Schiindehiitte et al.

[ REACTIVE DYESTUFFS CONTAINING A FIBER-REACTIVE ALKYLSULPHONYLPYRIMIDYL GROUP [75] Inventors: Karl-Heinz Schiindehiitte; Kersten Trautner, both of ,Leverkusen, Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Mar. 24, 1970 [21] App]. No.: 22,365

Related US. Application Data [63] Continuation of Ser. No. 512,542, Dec. 8, 1965,

abandoned.

[52] US. Cl. 260/146 D, 8/72 R, 8/50, 260/145 B, 260/146 T, 260/147, 260/153,

[51] Int. Cl...C09b 62/22, C09b 62/24, C09b 62/26 58 Field 61 Search, 260/146, 146 D, 146 T, 260/147, 152, 153, 154, 156, 157, 158, 162, 163, 242, 261, 262, 257, 256.4 N, 250 R,

Primary ExaminerFloyd D, Higel Attorney, Agent, or Firm-Plumley & Tyner [57] ABSTRACT Reactive dyestuffs particularly useful in the dyeing of textile materials containing hydroxyl groups or nitrogen, such as natural and regenerated cellulose, wool, silk, synthetic polyamides, and synthetic polyure- Dec. 10, 1974 thanes, are prepared and have the formula:

wherein R is hydrogen or a lower alkyl radical of l to 5 carbon atoms; A is a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, triazine, quinoline, phthalazine, cinnoline, phenazine, or phenanthridine radical which contains at least one lower alkyl sulfonyl, phenyl sulfonyl, benzyl sulfonyl, naphthyl sulfonyl, benzthiazolyl sulfonyl, thiazolyl sulfonyl, thiadiazolyl sulfonyl, oxazolyl sulfonyl, benzimidazolyl sulfonyl, 0r pyrimidyl sulfonyl, said sulfonyl radical containing no substituents or substituents selected from the class consisting of the bromine, chlorine, hydroxyl, nitro, cyano, sulfo, carboxyl, carboxy lower alkyl, lower carboalkyl, lower carboalkoxy, lower alkoxy, lower alkyl, lower alkyl sulfonyl amino and acetyl amino radical, said reactive sulfonyl substituent being linked to a carbon atom of the heterocyclic moiety A; and m represents a number from 0.5 to 8. The dyeings which can be obtained with the new dyestuffs are characterized by good to very good fastness properties, especially by excellent fastness to wet processing.

14 Claims, N0 Drawings in which F is the radical of an organic dyestuff; X is an alkylene radical, an arylene radical, SO

in which R is hydrogen or a monovalent organic substituent, said radical X is directly bonded to the radical A and is either directly or by means of a divalent bridging group connected to the dyestuff radical F; A is the radical of a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and which can contain fused carbocyclic rings, and m is a number of 0.5 to 8.

In the dyestuffs of the general formula (I), the radical A is, by definition, linked to the dyestuff radical F via the divalent radical X which, in turn, is bonded directly or through a bridging group to the dyestuff radical F. As divalent X radicals, those containing nitrogen are preferred, especially NH and --N(CI-l groups as well as sulfonamide and carbonamide groups. The amino or amide groups can carry further substituents, such as lower alkyl (preferably C to C aralkyl, cycloalkyl, or aryl groups, but preferably they are present in the form Nl-l which is not further substituted. The amino groups are, in turn, either linked directly, on the one hand, to the radical A and, on the other hand, linked either directly or via a further bridge member such as -SO or CO- (as in the case of the amide grouping already mentioned), or an alkylene group, an arylene, arylene-SO aryleneCO--, aryleneamino group, a urea group or a triazine or diazine ring, an arylene-amido-sylfonyl group or by other bridging groups to the aromatic radical F of the dyestuff. If such further bridge members contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl radicals, these also may contain reactive atoms or groupings, such as halogen atoms or sulfonyl substituents.

Similarly, other possible bridging radicals X, such as SO alkylene, (saturated or unsaturated) and arylene, are bonded on one side directly to the heterocyclic radical A and are linked, on the other side, either directly or via additional bridging groups with the radical F; such additional bridging members between X and F result, for example, in the following radicals being attached to the dyestuff radical F: OC-arylene-A; OC-alkylene-A; -OC--aralkylene-A; -OC- alkarylene-A; -O S-arylene-A; O Salkylene-A;

alkylene-A; -(R)NOC-aralkylene-A; (R)N--OC- alkarylene-A; (R)NOC-arylene-A; N=)t Naralkylene-A; N=N-arylene-A; and -(R)NO SA.

Suitable reactive sulfonyl substituents in the radical A are lower alkyl-sulfonyl radicals, preferably with 1-5 carbon atoms, such as methyl-sulfonyl, ethyl-sylfonyl, or propyl-sulfonyl radicals; aryl-sulfonyl radicals, such as phenyl-sulfonyl, ptoluene-sulfonyl, pchlor0phenylsulfonyl radicals; aralkyl-sulfonyl radicals, such as benzyl-sulfonyl and p-toluylmethyl-sulfonyl radicals; and also hetero-sulfonyl radicals, such as 2-benzothiazolesulfonyl.

The 6-membered heterocyclic ring A which contains at least one reactive sulfonyl subs'tituent, ie one that is split off under the known conditions for applying reactive dyestuffs is, for example, a monoazine, diazine, or triazine ring, such as pyridine, pyrimidine, pyridazine, pyrazine, thiazine, or an asymmetric or symmetric triazine ring, or a ring system of this type with one or more fused aromatic rings, such as a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine, or phenanthridine ring. The heterocyclic ring A is preferably one which contains one or more nitrogen atoms in the ring, as in the compounds mentioned above. Rings fused to the heterocyclic ring are, by definition, aromatic in nature and can be carbocyclic or heterocyclic in nature. The fused rings can be 5- or (ymembered. The heterocyclic 6-membered ring A is preferably a pyrimidine or symmetrical triazine ring.

The linkage of the heterocyclic ring A to X is either from the heterocyclic ring which carries one or more of the reactive sulfonyl substituents, or is from the carbocyclic or heterocyclic ring system fused to the 6- membered ring. In the case where the bridge member X is bonded to the heterocyclic ring which contains the reactive sulfonyl substituent or substituents, X is linked either to a carbon atom or to a hetero atom, among the latter preferably a nitrogen atom of the heterocyclic 6- membered ring. However, it is preferred to have X bonded to a carbon atom of the heterocyclic ring A.

As suitable heterocyclic rings A which contain at least one reactive sulfonyl substituent and may contain further rings fused to the heterocyclic ring, there may be mentioned, by way of example: 2-carboxy-methyl sulfonyl-4-pyrimidinyl, 2-methyl-sulfonyl-4-methyl-6- pyrimidinyl, 2-phenyl-sulfonyl-4-methyl--pyrimidinyl, 2-phenyl-sulfonyl-4-methyl- -chloro-6-pyrimidinyl, 2,4- bis-methyl-sulfonyl-6-pyrimidinyl, 2,4-bis-methylsulfonyl-5-sulfamidyl-pyrimidine, v3-phenyl-sulfonyl-6- pyridazinyl, 3methyl-sulfonyl-4-methyl-6-pyridazinyl, 2,5-bis-methyl-sulfonyl-6-pyrazinly, l-methyl-sulfonyl- 3-triazinyl, l-methyl-sulfonyl-3-( 3 sulfophenylamino)-5-triazinyl, 1-methyl-sulfonyl-3-(2'- hydroxyethylamino)-5-triazinyl, l-methyl-sulfonyl-3- amino-S-triazinyl, l-methyl-sulfonyl-3-methoxy-5- triazinyl, l-methyl-sulfonyl3-(2-benzthiazolyl)-thio- 5-triazinyl, l -(4-methyl-phenyl-sulfonyl )-3-phenyl-5- triazinyl, as well as 2-methyl-sulfonyl-4-quinazolyl, 2- methyl-sulfonyl-4-pyrimidinyl, 2-phenyl-sulfonyl-4- pyrimidinyl, 2-methyl-sulfonyl-4-methyl-o-pyrimidinyl, 2*methyl-sulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2- carboxymethyl-sulfonyl-4-methyl-5-chloro-6- pyrimidinyl, 3-(4-nitrophenyl)-su1fonyl-6-pyridazinyl, 5-chloro- 6-methyl-sulfonyl-4-pyridazinyl, l-phenylsulfonyl-3-methoxy-5-triazinyl, Il,3-bis-phenyl-sulfo- 3 nyl-S-triazinyl, lmethyl-sulfonyl-3-phenoXy-5- triazinyl, lmethyl-sulfonyl-3phenyl-Striazinyl.

The reactive sulfonyl substituent or substituents can contain in the aryl, alkyl, or hetero residues additional ionic or non-ionic groups, such as carboxy (e.g. in the form of carboxy-methyl), sulfo, hydroxyl, nitro, or halogen (Cl, Br) groups; the following substituted sulfonyl groups may be mentioned as examples: carboxy-methyl-sulfonyl, chloromethyl sulfonyl, B-chloroethyl sulfonyl, ,B-hydroxyethyl sulfonyl, B-sulfoethyl sulfonyl, ,B-methoxyethyl sulfonyl, B-ethoxyethyl sulfonyl, B-propoxyethyl sulfonyl, sulfobutyl sulfonyl, B-carboxyethyl sulfonyl, ,B-cyanoethyl sulfonyl, cyanomethyl sulfonyl, B-carbo lower alkoxyethyl sulfonyl (having 1 to 3 carbon atoms in the lower alkoxy residue, ,8-carbo lower alkoxy methyl sulfonyl, methyl sulfonyl methyl sulfonyl, Bmethyl sulfonyl ethyl sulfonyl, ethyl sulfonyl methyl sulfonyl, B-ethyl sulfonyl ethyl sulfonyl, B-carboxy vinyl sulfonyl, B-chloro vinyl sulfonyl, a, B- or B,B-dichlorovinyl sulfonyl, sulfophenyl sulfonyl, mor p-methylor ethyl-phenyl sulfonyl, o-, mor pchloroor bromophenyl sulfonyl, 2,4- or 2,5-dichloroor dibromophenyl sulfonyl, p-carboxyphenyl sulfonyl, o,p-dicarboxyphenyl sulfonyl, o-, mor pmethoxyphenyl sulfonyl, o-methoxy-p-chloropheny sulfonyl, o-methyl-p-chlorophenyl sulfonyl, o-, mor p-nitrophenyl sulfonyl, 2,4-dinitrophenyl sulfonyl, paminophenyl sulfonyl, p-acetylaminophenyl sulfonyl and other o-, mor p-acylaminophenyl sulfonyl, sulfonaphthyl-lor 2-sulfonyl, substituted naphthyl sulfonyl radicals carrying substituents as indicated hereinbefore for the substituted phenyl sulfonyl radicals. Other unsubstituted reactive sulfonyl radicals are those of the heterocyclic series, such as for instance benzthiazolyl sulfonyl, thiazolyl sulfonyl, thiadiazolyl sulfonyl, oxazolyl sulfonyl, benzimidazolyl sulfonyl, pyrimidyl sulfonyl as well as substitution products of these heterocyclic reactive sulfonyl radicals.

Of the large number of possible and suitable bridge members XA, including bridging members to the radical F, the following may be mentioned by way of example: NH-A, N(CH )A, N(C l-l )A, N(C H )A, CONl-lA, SO Nl-l-A, N- HO SA, --CON(Cl-l )A, SO N(CH )A,

(CH )NO SA, and the corresponding N-ethylm zl lim 1 and the corresponding N-alkyl (l5 C)-amides or amines N H-A Oorl as well as the corresponding N-alkyl 1-5 C)-amides or amines of the said compounds.

A further suitable bridge member is the azo grouping N=N. In a special case the new dyestuffs correspond to the formula in which F is the residual constituent of an azo dyestuff, A has the meaning specified above, and k stands for the number 1 or 2; F is in this formula, for example, the radical of a coupling component, but F can also be any other aromatic carbocyclic or heterocyclic radical which serves for the synthesis of the azo dyestuff (ll), eg by condensation.

The new dyestuffs may belong to a great variety of .classes, e.g. to the series of metal-free or metalin which B and D are aromatic, carbocyclic, or heterocyclic radicals, and in particular where B is the radical of a carbocyclic diazo component of the benzene or naphthalene series, and D is the radical of an enolic or phenolic coupling component, e.g. of a S-pyrazolone, an acetoacetic acid arylamide, an oxynaphthalene or an aminonaphthalene, etc.; B and D can moreover contain any substituent customary in azo dyestuffs, including further azo groups; R, is a substituent or, preferably, a hydrogen atom, Q is a direct bond or an SO group, m denotes an integer, preferably the number 1 or 2, and A is the radical of a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and may contain fused carbocyclic rings. It is to be understood that in the foregoing Formula (III) the radical corresponds to the radical X in Fonnula (I).

Especially valuable dyestuffs of this series are those which are water-soluble and, in particular, those containing sulfonic acid and/or carboxylic acid groups. The azo dyestuffs can be metal-free as well as metalcontaining, the cooper, 1:2 or 1:1 chromium and cobalt complexes being the most interesting metal complexes.

NHz

In this formula L is hydrogen or a substituent, the sulfonic acid group being the preferred substituent, p is the number 1, 2, or 3, R is a substituent or, preferably, hydrogen, Q is a direct bond or an SO -group, and A is a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and may contain fused carboxcyclic rings. It is to be understood that in the foregoing Formula (IV), the radical corresponds to the radical X in Formula (I).

Also in the range of these dyestuffs, the water-soluble products are preferred because of their excellent suitability for the dyeing and printing of cellulosecontaining fibers; the dyestuffs substituted by sulfonic acid groups have proved particularly suitable for this purpose.

3. Azaporphin dyestuffs having the formula In this formula Pc stands for the :radical of a phthalocyanine, e.g. of a copperor nickel-phthalocyanine or a tetraphenyl-copper or -nickel-phthalocyanine, L stands for hydrogen or a substituent, the sulfonic acid group being preferred as substituent, r stands for the number 1 or 2, q for the number 0, l or 2, R for a substituent or, preferably, hydrogen, *0 for a direct bond or a SO -group, A for a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and may contain further fused carbocyclic rings, and m stands for a number of 0.5 to 4. The phthalocyanine radical Pc can obviously contain further substituents, especially sulfonic acid and/or N-substituted (e. g. by lower alkyl) and/or N-unsubstituted sulfonamide groups. It is to be understood that in the foregoing Formula (V), the radical l B1 A corresponds to the radical X in Formula (I).

Water-soluble phthalocyanine dyestuffs of the formula (V) which are preferred for application to cellulose-containing materials are particularly those which carry sulfonic acid groups in the radical Pc and optionally, in addition, as the substituent L.

The foregoing discussion of suitable azo, anthraquinone, and azaporphin dyestuffs and heterocyclic ring systems A is not intended to represent a limitation of the general formula, either in respect of the possibilities of preparing such dyestuffs within the scope of thegeneral formula (I), or with regard to the valuable technical properties of applying these products. The new dyestuffs can, moreover, contain any substituent customary in dyestuffs, such as sulfonic acid, carboxylic acid, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogen, hydroxyl, alkoxy, thioether, azo groups, and the like. The dyestuffs may also contain further groups capable of fixation, such as monoor dihalo-triazinyl-amino, mono-, di-, or trihalo pyrimidinyl-amino, 2,3-dihaloquinoxaline-6-carbonylor -6-sulfonylamino, l ,4-dihalo-phthalazine6- carbonylor -6-sulfonyl-amino, 2-halobenzothiazole-5- carbonyl or -5-sulfonyl-amino, esterified sulfonic acid oxalkylamide or oxalkyl-sulfone groups, sulfofluoride, halo-alkylamino, acryloylamino, haloacylamino groups, and the like.

The new dyestuffs of the formula (I) are obtained by introducing, according to known methods, into dyestuffs or dyestuff intermediates, a group -XA wherein X is a group X linked directly with the radical A on one side and either directly or over a further bridging member,

on the other side, with the radical F. The term R represents hydrogen or a substituent, arylene an arylene residue, and alkylene a lower alkylene residue. The radical A is a 6-membered heterocyclic ring and contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and which can contain further fused carbocyclic rings. ln the case where dyestuff intermediates are used, these are subsequently converted into the desired end dyestuffs. The introduction of the XA group into the dyestuffs or dyestuff intermediates can be carried out by various methods of preparation. Thus, amino or amide group-containing dyestuffs or dyestuff intermediates which exhibit one reactive hydrogen atom at the amine or amide nitrogen, can be reacted with compounds of the general formula in which A represents a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and which can have fused thereto carbocyclic rings, and Y is a radical which can be split off as anion, and, if dyestuff intermediates are used, then converted in a suitable manner into the desired end dyestuffs. Of the reactive substituents Y which can be split off as anionic radicals, chlorine, bromine, and sulfonyl substituents are preferred. Further suitable radicals which can be split off as anions are, for example, fluorine, M (M being H or a metal cation), quaternary ammonium groups, alkylmercapto, nitrile, alkoxy, or aryloxy groups.

Heterocyclic compounds of the formula (VI) which are suitable for the reaction are, for example, 2- carboxymethylsulfonyl-4-chloropyrimidine,

2,4-bismethylsulfonyl-6-methyl-4-chloropyrimidine, methylsulfonyl-6-methylpyrimidine, 2,6-bisphenylsulfonyl-4-methyl-5-chloropyrimidine, 2,4,6-

tris-methylsulfonyl-pyrimidine, 2,4-bis-methylsulfonylpyrimidine-S-sulfonic acid chloride, 2,5,6-trismethylsulfonyl-pyrazine, l,3-bis-methylsulfonyl-2,4,6- triazine, I ,3-bis-methylsulfonyl--( 3 '-sulfophenylamino)-2,4,6,triazine, l,3-bis-methylsulfonyl-5- phenoxytriazine, l,3-bis-methylsulfonyl-S-trichloroethoxytriazine and numerous other 1,3-bis-methylsulfonyl-2,4,6-triazines substituted in the 5-position, 2,4-bismethylsulfonyl-quinazoline, 2,4-bis-phenylsulfonylquinoline, 2-methylsulfonyl-4-chloropyrimidine, 2- chloromethylsulfonyl-4-chloropyrimidine, 2- phenylsulfonyl-4-chloropyrimidine, 2,6-bismethylsulfonyl-4-methyl-5-chloropyrimidine, 2- methylsulfonyl-4-methyl-5,o-dichloropyrimidine, 2,6- bis-methylsulfonyl- -methyl-5-bromopyrimidine, 2- methylsulfonyl-4-methyl-6-chloro-pyrimidine-5- sulfonic acid chloride, 4,6-bis-methyl-methylsulfonyl- 5-chloropyridazine, 3,6-bis-phenylsulfonylpyridazine, 3-methylsulfonyl-6-chloro-pyridiazine, 3,6-bismethylsulfonyl-4-methyl-pyridazine, and the bromoderivatives of the named chloro compounds.

The reaction of the amino or amide group-containing dyestuffs or dyestuff intermediates with heterocyclic compounds of the formula (V1) is carried out, depending on the type of starting compounds employed, in an organic, aqueous-organic or aqueous medium at temperatures of l0C to +80C, preferably in the presence of alkaline condensing agents, such as pyridine,

aqueous alkali metal carbonate, or alkali metal hydroxide solutions.

When dyestuff intermediates are used, the condensation products obtained are converted in known manner into the desired end dyestuffs. This process is mainly of interest for the preparation of azo dyestuffs in that, for example, a diazo and/or coupling component exhibiting a reactive amino or amide group is first condensed with the reactive component (VI), and the resultant intermediate product is subsequently converted into an azo dyestuff by diazotiyation, and/or coupling, and/or condensation. This azo dyestuff can be subjected to further conversion reactions customary in azo dyestuffs, e.g. acylation, condensation, reduction, and metallization. Also in the preparation of other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (VI) can first be carried out with an intermediate product, e.g. with m-phenylene-diamine or a m-phenylene-diamine-sulfonic acid and the resultant reaction product subsequently further condensed, e.g. with bromoamino acid lamino-4-bromoanthraquinone-Z-sulfonic acid) to form a reactive anthraquinone dyestuff, or with a copperor nickelphthalocyanine-sulfonic acid halide to form a reactive phthalocyanine dyestuff,

Another method of preparing the new dyestuffs of the formula (I) consists in that amino or amide groupcontaining dyestuffs or, in particular, dyestuff intermediates which exhibit an exchangeable hydrogen atom at the amino or amide group, are reacted with compounds of the general formula in which A represents a 6-membered heterocyclic ring which can contain further fused carbocyclic rings, Z is a radical which can be split off as anion, with the exception of a sulfonyl radical, and t denotes the number 2 or a number greater than 2, while replacing one of the radicals Z which can be split off an anion, that the remaining radical or radicals Z are subsequently converted in known manner into reactive sulfonyl substituents and, if dyestuff intermediates are used, these transformed into the desired end dyestuffs.

The exchange of one or more subsituents Z capable of being split off an anion, e.g. of halogen atoms, for reactive sulfonyl substituents can be effected, e.g. by reacting the compounds with alkylor aryl-sulphinates or, if Z represents, for example, an alkylmercapto or arylmercapto group which can be split off as anion, by transforming the latter by means of suitable oxidizing agents, such as hydrogen peroxide, hypohalides or permanganates, into the corresponding sulfonyl radicals.

The dyestuffs obtainable by the various processes described above can be subjected, as has already been mentioned for some cases, to further reactions customary for dyestuffs, in that, for example, metallizable dyestuffs are treated with metal-yielding agents, especially chromium, cobalt, copper or nickel salts; dyestuffs containing reducible groups, especially nitro groups, are reduced; dyestuffs containing acylatable groups, especially acylatable amino groups, are acylated; or dyestuffs are subsequently treated with sulfonating agents, such as chlorosulfonic acid, thionyl chloride, oleum or S0 in chlorinated hydrocarbons, in order to introduce further sulfonic acid groups into the products. The lastmentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs.

Depending on the number of reactive groupings in the dyestuff radical or dyestuff intermediates, preferably -HNR- groupings, which are suitable for the conversion, one or more groupings of the formula X-A can be incorporated in the dyestuffs. In the majority of cases the number m will not exceed 4, but dyestuffs with more than 4, e.g. up to 8 groupings of the formula XA, especially those of higher molecular structure, can also be synthesized.

If the dyestuffs prepared according to the invention contain groups forming metal complexes, then they can be converted into their metal complex compounds by the action of metal-yielding agents, e.g. copper, nickel, chromium, or cobalt salts. They can also be subjected to other customary conversion reactions, such as diazotization, coupling, acylation, and condensation.

For the reaction of amino group-containing dyestuffs with reagents AY of the formula (VI) one employs, preferably for example, aminoazo dyestuffs of the formeaning, or aminoanthraquinone dyestuffs having the formula (VIII) wherein L, R,, and p have the above-indicated meaning, or amino group-containing phthalocyanine dyestuffs of the formula condensed with the reactive component A-Y and subsequently transformed into the final dyestuffs in the usual manner. The method of employing dyestuff intermediates is of paticular interest in the preparation of azo dyestuffs and of anthraquinone: and phthalocyanine dyestuffs. In the 2120 dyestuffs, one proceeds in such a manner that a diazo component or a coupling component which contains a reactive amino group is condensed with the reactive component of formula (VI) and subsequently built into the desired azo dyestuff through coupling. The resulting product can further be metallized or diazotized and thereby transformed into a disazo or polyazo dyestuff. In the anthraquinone dyestuffs, one can, for example, condense a diaminoaryl compound in which one amino group is protected, e.g. an acylamino bond, through the second amino group with a reactant component of formula (VI) and subsequently transform a protected amino group into a free amino group such as, for example, by saponification, and condense the resulting product with, for example, l-amino-4-bromoanthraquinone-2-sulfonic acid to a valuable anthraquinone dyestuff type. For the preparation of the phthalocyanine dyestuffs, one can prepare a mono-condensation product of a diaminoaryl compound with dyestuffs and, condense this product with, for example, copperor nickelphthalocyanine-sulfonic acid-halides, whereby simultaneously or subsequently other amino compounds such as ammonia, aliphatic amino compounds, and/or aromatic amino compounds can also be employed therewith. One obtains, using this procedure, phthalocyaninesulfonamide dyestuffs which contain a certain amount of sulfonaryl-amido groups which carry the reactive groups and also contain a certain amount of non-reactive sulfonamido groups and/or free sulfonic acid groups.

A particularly preferred group of reactive dyestuffs falling within the scope of formula (I) are those having the general formula wherein F is the residue of an organic dyestuff, X, an amino group, A, the residue of a pyrimidine ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring, and m is a number from 0.5 to 8.

In the dyestuffs of the general formula (XI), the radical A, is by definition bonded to the dyestuff radical F by means of an amino group X,. The amino group can contain further substituents such as lower alkyl groups (preferably C, to C aralkyI-, cycloalkyl-, or aryl groups, but exists preferably in the unsubstituted form NI-I-. The amino groups are, on the other hand, directly bonded to aromatic ring carbon atoms of the dyestuff.

The reactive sulfonyl substituents are preferably lower alkylsulfonyl groups which contain, preferably, from I to 5 carbon atoms, such as methylsulfonyl-, ethylsulfonylor propylsulfonyl-. Other suitable reactive sulfonyl substituents are arylsulfonyl groups such as phenylsulfonyl, p-toluylsulfonyl, p-chlorophenylsulfonyl groups; aralkylsulfonyl groups such as benzylsulfonyl and p-toluylsulfonyl groups, and also heterosulfonyl groups such as 2-benzothiazolylsulfonyl as well as those mentioned hereinbefore.

Suitable pyrimidine groups A, which contain at least one reactive sulfonyl substituent are, for example, 2-

carboxy-methylsulfonyl-4-pyrimidinyl, 2- methylsulfonyl-4-methyl-6-pyrimidinyl, 2- phenylsulfonyl-4-methyl-6-pyrimidinyl, 2- phenylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2,4-

bis-methylsulfonyl-6-pyrimidinyl, 2-methylsulfonyl-4- methyl--nitro-6-pyrimidinyl, 2-methylsulfonyl-5- cyano-4-pyrimidinyl, 2-methylsulfonyl-4-carboxy-6- pyrimidinyl, and 2-ethylsulfonyl-5-sulfo-4-pyrimidinyl, as well as those mentioned hereinabove.

The reactive sulfonyl substituent or substituents attached to the ring A, can contain further ionic or nonionic groups such as, for example, carboxy (e.g. in the form of carboxy methyl), hydroxy, nitro, halogen (Cl, Br), sulfonic acid or sulfo groups, as well as groups mentioned hereinabove.

The dyestuffs (XI) may belong to a great variety of classes, e.g. to the series of metal-free or metalcontaining monoor polyazo dyestuffs; metal-free or metal-containing azaporphin dyestuffs, such as 1- nickel-phthalocyanine dyestuffs; of the anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone, and dibenzanthrone dyestuffs; and polycyclic condensation compounds of anthraquinone, benzanthrone, and dibenzanthrone compounds. Within the range of these dyestuff classes, dyestuffs of the following general formulae are particularly valuable.

l. Azo dyestuffs having the formula (XII) wherein B, D, R,, and m have the meanings indicated for the dyestuffs for formula (III) and A, is a pyrimidine ring radical which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring. Particularly valuable dyestuffs of this series are those which are water-soluble and, more particularly, those which contain sulfonic acid and/or carboxylic acid groups. The azo dyestuffs can be metal-free as well as metal-containing. Metal complexes which are of particular interest are those of copper, chromium, and cobalt.

(XIII) Po s O NII- i R, in (XIV) in which Pc, L, q, r, m", and R, have the meanings indicated in formula (V) and wherein A, is a pyrimidine radical which contains at least one sulfonyl substituent linked to a carbon atom of the heterocyclic ring. The phthalocyanine radical Pc can obviously contain further substituents, especially sulfonic acid and sulfonamide groups. Water-soluble phthalocyanine dyestuffs of the formula (XIV), which are preferred for application to cellulose-containing materials, are particularly those which carry sulfonic acid groups in the radical Fe and, optionally, in addition, as the substituent L. The foregoing discussion of suitable azo, anthraquinone, and azaporphin dyestuffs, and heterocyclic ring system A is not intended to represent a limitation of the general formula, either in respect to the possibilities of preparing such dyestuffs within the scope of the general formula (I) or with regard to the valuable technical properties of applying these products.

Particularly valuable dyestuffs, from a technical standpoint, are those having the general formulas (XII), (XIII), and (XIV), in which the residue corresponds to the following particular formula R, xv

wherein R, is hydrogen or an alkyl residue containing from 1 to 3 carbon atoms, one of the groups R, or R, is an -SO Mgroup, wherein M is an alkyl, aralkyl, or aryl group, and wherein the other group R or R, can also be an -SO M-group or hydrogen, alkyl, aralkyl, aryl, SO ,H, COOI-I, -COO-alkyl, -Cl, --Br, or CN; and wherein R, is hydrogen or a substituent such as alkyl, aralkyl, aryl, SO H, COOH, COO-alkyl,

-Cl, -Br, -CN, nitro, carbonamide, or sulfonarnide, the alkyls having 1-4 carbon atoms.

Of particularly great importance are those dyestuffs having the formulas (XII), (XIII), and (XIV), in which the residue A is 2-methylsulfonyl-5-chloro-6- methylpyrimidinyl-4. This reactive component is introduced by reaction of the amino group-containing dyestuff with, for example, 2-methylsulfonyl-j4,5-dichloro- 6-methylpyrimidine. The new dyestuffs of formula (XI) can, moreover, contain any substituent customary in dyestuffs, such as sulfonic acid, carboxylic acid, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogen, hydroxyl, alkoxy, thioether, azo-groups and the like. The dyestuffs may also contain further groups capable of fixation such as monoor dihalotriazinyl-amino, mono-, di-, or trihalo-pyrimidinylamino, 2,3-dihaloquinoxaline-6-carbonyl or -6- sulfonylamino, l,4-dihalophthalazine-6-carbonylor -6-sulfonyl-amino, 2-halobenzothiazole-S-carbonyl or -5-sulfonyl-amino, esterified sulfonic acidoxalkylamide or oxalkyl-sulfone groups, sulfofluoride, halo-alkylamino, acryloylamino, haloacylamino groups and the like.

The novel dyestuffs of formula (XI) are obtained by introducing, according to known methods, into dyestuffs or dyestuff intermediates at least one pyrimidinyl amino group which contains at leastone sulfonyl substituent linked to a carbon atom of the pyrimidine ring and which is bonded to a ring carbon atom of the aryl nucleus of the dyestuff or dyestuff precursor and which, in the event that a dyestuff intermediate is employed, is then transformed into the desired final dyestuff. The pyrimidinyl amino group which contains at least one reactive sulfonyl substituent can be introduced into the dyestuff or dyestuff intermediate by reacting amino group-containing dyestuffs or dyestuff intermeidates which contain a reactive hydrogen atom in the amino nitrogen by reaction by a compound having the general formula wherein A is a pyrimidine group which contains at least one reactive sulfonyl substituent linked to a carbon atom of the heterocyclic ring and in which Y is a radical which can be split off as an anion.

Of the reactive substituents Y which can be split off as anionic radicals, chlorine, bromine, and sulfonyl substituents are preferred. Further suitable radicals which can be split off as anions are, for example, F, 80 M (M being H or a metal cation), quaternary ammonium groups, alkylmercapto, nitrile, alkoxy or aryloxy groups. A particularly preferred reactive component of the formula A Y is 2-methylsulfonyl-4,5- dichloro-6-methylpyrimidine, in the condensation of which with amino group-containing dyestuffs or dyestuff intermediates, surprisingly the chlorine in the 4- position reacts with the -N-II in groups.

Heterocyclic compounds corresponding to formula (XVI), which are useful for the reaction, include, for example, 2-carboxymethylsulfonyl-4- chloropyrimidine, 2-methylsulfonyl-6'methyl-4- chloropyrimidine, 2,4-bis-methylsulfonyl-6- methylpyrimidine, 2,6-bis-phenylsulfonyl-4-methyl5- chloropyrirnidine, 2,4,6-tris-methulsulfonylpyrimidine, 2,4,5,6-tetramethylsulfonyl'pyrimidine, 2- methylsulfonyl-4-methyl-5-nitro-6-chloropyrimidine, 2-methylsulfonyl-4,5-dimethyl-6-chloropyrimidine, 2- ethylsulfonyl-4-methyl-5,6-dichloropyrimidine, 2- methylsulfonyl-4,o-dichloropyrimidine, 2,4,6-trismethylsulfonyl-S-chloropyrimidine, Z-methylsulfonyl- 4-carboxy-6-chloropyrimidine, 2methylsulfonyl-4- chloropyrimidine-S-sulfonic acid, and 4,6-bis methylsulfonyl-pyrimidine, as well as those listed on page 11 hereinabove. The reaction of the amino groupcontaining dyestuffs or dyestuff intermediates with the heterocyclic compounds of formula (XVI) is carried out, depending on the type of starting compounds employed, in an organic, aqueous-organic, or aqueous medium at temperatures of -l0 to +C, preferably in the presence of alkaline condensing agents, such as pyridine, aqueous alkali metal carbonate, or alkali metal hydroxide solutions.

When dyestuff intermediates are used, the condensation products obtained are converted in known manner into the desired end dyestuffs. This process is mainly of interest for the preparation of azo dyestuffs in that, for example, a diazo and/or coupling component exhibiting a reactive amino group is first. condensed with the reactive component (XVI) and the resultant intermediate product is subsequently converted into an azo dyestuff by diazotization, and/or coupling, and/or condensation. This azo dyestuff can be subjected to further conversion reactions customary in azo dyestuffs, e.g. acylation, condensation, reduction, and metallization. Also in the preparation of other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (XVI) can first be carried out with an intermediate product, e.g. with m-phenylenediamine or a m-phenylenediaminesulfonic acid and the resultant reaction product subsequently further condensed, e.g. with bromoamino acid (1-amino-4-bromo-anthraquinone-2sulfonic acid) to form a reactive anthraquinone dyestuff or with a cop peror nickel-phthalocyanine-sul'fonic acid halide to form a reactive phthalocyanine dyestuff.

Another method of preparing the new dyestuff of the formula (XI) consists in that amino group-containing dyestuffs or, in particular, dyestuff intermediates which exhibit an exchangeable hydrogen atom at the amino group, are reacted with compounds of the general formula wherein A is a pyrimdine rin'g, Z is a radical which can be split off as anion, with the exception of a sulfonyl radical, and t denotes the number 2 or a number greater than 2, while replacing one of the radicals Z which can be split off as an anion, the remaining radical or radicals Z are subsequently converted in known manner into sulfonyl substituents and, if dyestuff intermediates are used, these transformed into the desired end dyestuffs.

The exchange of one or more substituents Z capable of being split off as anion, e. g. of halogen atoms, for sulfonyl substituents can be effected, e.g. by reacting the compounds with alkylor alkyl-sulfonates, or if 2 represents, for example, an alkylmercapto or arylmercapto group which can be split off as anion, by transforming the latter by means of suitable oxidizing agents such as hydrogen peroxide, hypohalide, or perrnanganates, into the corresponding sulfonyl radicals.

The dyestuffs (XI), obtainable by the various processes described above, can be subjected, as has already been mentioned for some cases, to further reactions customary for dyestuffs, in that, for example, metallizable dyestuffs are treated with metal-yielding agents, especially chromium, cobalt, copper or nickel salts; dyestuffs containing acylatable groups, especially acylatable amino groups, are acylated; or dyestuffs are subsequently treated with sulfonating agents, such as chlorosulfonic acid, thionylchloride, oleum or S0 in chlorinated hydrocarbons, in order to introduce further sulfonic acid groups into the products. The last mentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs.

Depending on the number of reactive groupings in the dyestuff radical or dyestuff intermediates, preferably I-INR groupings (R being hydrogen or a substituent such as a lower alkyl group), which are suitable for the conversion, one or more groupings of the formula XA can be incorporated in the dyestuffs. In the majority of cases, the number m will not exceed 4, but dyestuffs with more than 4, eg up to 8 groupings of the formula ITI A1 HI NII] Ll,

wherein B, D, R and m have the meanings indicated above, aminoanthraquinone dyestuffs having the formula NII R (IX) (VIII) I in (X) wherein Pc, L, R q, r, and m have the aboveindicated meanings. The resulting condensation products correspond to the general formulas (I) and (XII) for the novel dyestuffs of the present invention. These dyestuffs can be subjected to further reactions of which, in particular, the subsequent sulfation of the anthraquinone and phthalocyanine dyestuffs is frequently of interest. Instead of employing the preformed amino group-containing dyestuffs of formula (VIII), (IX), and (X), amino group-containing precursors for the preparation of these dyestuffs can also be employed. These are first condensed with the reactive component A,Y and subsequently transformed in known ways to the final dyestuffs. This process of proceeding via the dyestuff intermediate is of particular interest in the preparation of azo dyestuffs, anthraquinone dyestuffs, and

phthalocyanine dyestuffs. In the preparation of azo dyestuffs, a diazo and/or coupling component exhibiting a reactive amine group is first condensed with the reactive component (XVI) and subsequently converted into the desired azo dyestuff by coupling. The resulting product can further be post-metallized or diazotized and transformed into a disazo or polyazo dyestuff. In the anthraquinone dyestuff series one can, for example, condense a diaminoaryl compound in which one of the amino grops is protected such as in the form of an acylamino group with a reactive component (XVI) at the second amino group, then transform the protected amino group into a free amino group, for example, through saponification and condense the resulting product with, for example, l-amino-4-bromoanthraquinone-Z-sulfonic acid to a valueable anthraquinone dyestuff. In the preparation of phthalocyanine dyestuffs one can, similarly as in the anthraquinone dyestuffs, form the mono-condensation product of a reactive component A,Y with a diaminoaryl compound and subsequently condense such with copperor nickel-phthalocyanine-sulfonic acid halides while simultaneously or subsequently adding other amino compounds such as ammonia, aliphatic amino compounds and/or aromatic amino compounds. Employing the described method, one obtains phthalocyanine sulfonamide dyestuffs which contain a certain percentage of sulfonarylamide groups which are bonded to the reactive group and, in addition, a certain percentage of nonreactive sulfonamide groups and/or free sulfonic acid groups.

A particularly valuable class reactive dyestuffs within the scope of the novel dyestuffs of formula (I) has the formula m (XVIII) in which F is an organic dyestuff residue, X and amino group, Z a halogen atom, Y hydrogen, an alkyl or a substituted alkyl group, R an aliphatic, carbocyclic or heterocyclic substituent, and in which m is a number from I 0.5 to 8. In the dyestuif of the general formula (XVIII) the pyrimidine group is by definition connected by means of an amino group to the dyestuff residue. The amino group can contain further substituents such as lower alkyl (preferably C to C aralkyl, cycloalkyl or aryl groups, but preferably exists in the unsubstituted form of Nl-I-.

The amino group is, in turn, directly bonded to an aromatic ring carbon atom of the dyestuff or to an alkylene group.

Reactive sulfonyl substituents SO R, located in the 2-position of the pyrimidine ring, include lower alkylsulfonyl groups having, preferably from 1 to 5 carbon atoms, such as methylsulfonyl, ethylsulfonyl, or propylsulfonyl groups, arylsulfonyl groups such as phenylsulfonyl, p-toluylsulfonyl, p-chlorophenylsulfonyl groups; aralkylsufonyl groups such as benzylsulfonyl and p-toluylmethylsulfonyl groups; and also heterosulfonyl groups such as 2-benzothiazolysulfonyl. The reactive sulfonyl substituent or substituents can contain in the aryl, alkyl or hetero residues, additional ionic or nonionic groups such as carboxy, nitro, halogen (Cl, Br), sulfonic acid or sulfonic groups. Preferred halogen atoms Z are chlorine and bromine, and preferred substituents Y, aside from hydrogen include lower alkyl groups such as methyland ethyland lower substituted alkyl groups such as halogenmethyl groups, for example, monochloromethyl, bromomethyl, dichloromethyl, and trichloromethyl, carboxy methyl groups, carboalkoxy methyl groups such as carbomethoxy methyl and carboethoxy methyl groups, as well as cyano methyl groups.

Suitable pyrimidine components which contain in the 2-position a reactive sulfonyl substituent include, for

example, Z-methylsulfonyl-S-chloro-4-primidinyl, 2- methylsulfonyl 5-bromo-4-pyrimidinyl, 2- methylsulfonyI-S-chloro-6-methyl-4-pyrimidinyl, 2- methylsulfonyl-S-bromo-6-methyl-4-pyrimidinyl, 2-

methylsulfonyl-S-chloro-6-chloromethyl-4- pyrimidinyl, 2-phenyIsuIfonyl-5-chloro-4-pyrimidinyl, 2 phenylsulfonyl5-chloro-6-methyl-4-pyrimidinyl, 2- phenylsulfonyl-S-bromo-6-methyl-4-pyrimidinyl, 2- methylsulfonyl-5-chloro-6-carboxymethyl-4- pyrimidinyl, or Z-carboxymethylsulfonyl-5-chloro-6- methyl-4-pyrimidinyl, as well as those already mentioned on page 4 hereinabove. The dyestuffs of formula (XVIII) can belong to a great variety of classes, eg to the series of metal-free or metal-containing monoor polyazo dyestuffs; metal-free or metal-containing azaporphin dyestuffs such as copperor nickelphthalocyanine dyestuffs; of the anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone, and dibenzanthrone dyestuffs; and polycyclic condensation compounds of anthraquinone, benzanthrone, and dibenzanthrone compounds. Within the range of these dyestuff classes, dyestuffs of the following general formulae are particularly valuable. 1. A20 dyestuffs having the formula (XIX) N o-sogn N (la) wherein R, Z, and Y have the meanings indicated in formula (XVIII). Preferred radicals (Ia) are, for example, 2-methyIsulfonyl-5-chloro-6-methylpyrimidinel ,3 )-yl4 and Z-methylsulfonyl-S-monochloropyrimidine*(l,3)-yI-4, and the corresponding bromo compounds. Especially valuable dyestuffs of this series are those which are water-soluble and, in particular, those containing sulfonic acid and/or carboxylic acid groups. The azo dyestuffs can be metal-free as well as metalcontaining, the copper, chromium, and cobalt complexes being the most interesting metal complexes.

Important azo dyestuffs are, for example, those of the benzene-azo-naphthalene, benzene-azo l -phenyl-5- pyrazole, benzene-azdaminonaphthalene, naphtha]ene-azo-naphthalene, naphthalene-azo- I phenylpyrazolone-S, and stilbene-azo-benzene series,

the dyestuffs containing sulfonic acid groups being,

again, preferred. In the case of metal complex azo dye stuffs, the groups linked to the metal complex are, preferably, in the o-position to the azo groups, eg in the form of o,o'-dihydroxy, o-hydroxy-o'-carboxy, ocarboxy-o'-amino, and ohydroxy-o-aminoazo groupings. 2. Anthraquinone dyestuffs having the formula wherein L, p, and R have the meanings indicated in formula (IV) and A is a heterocyclic residue having the formula wherein R, Z, and Y have the meanings indicated in formula (XVIII). Preferred radicals (Ia) are, for example, 2-methylsulfonyl-5-chloro6-methylpyrimidine- 1,3 )-yl-4 and Z-methylsulfonyl-S-monochloropyrimidine-(l,3)-yl-4, as well as the corresponding bromo compounds.

Also in the range of these dyestuffs, the water-soluble products are preferred because of their excellent suitability for the dyeing and printing of cellulosecontaining fibers; the dyestuff substituted by sulfonic acid groups having proved particularly suitable for this purpose.

3. Azaporphin dyestuffs having the formula wherein Pc, L, r, q, and R have the meanings indicated in formula (V), and A in a heterocyclic radical having the formula mula (XXI) which are preferred for application to cellulose-containing materials are, particularly, those which carry sulfonic groups in the radical Po and, optionally, in addition, as the substituent L.

The foregoing discussion of suitable azo, anthraquinone, and azaporphin dyestuffs, as well as the pyrimidine group, is not intended to represent a limitation of the general formula, either in respect to the possibilities of preparing such dyestuffs within the scope of the general formula (XVIII) or with respect to the valuable technical properties of applying these products. The dyestuffs having the formula (XVIII) can, moreover, contain any substituent customary in dyestuffs, such as sulfonic acid, carboxylic acid, and substituted sulfonamide or carbonamide groups, disulfimide groups, N-sulfonyl-N-carbonylimide groups, alkylsulfonic, arylsulfonic, alkylamino, arylamino, aralkylamino, nitro, cyano, halogen, hydroxy, esterified hydroxy groups, alkoxy, thioether, alkyl, aryl, aralkyl, trifluoralkyl, acylamino, azo groups and the like.

The dyestuffs can also contain further groups capable of fixation, such as monoor dihalotriazinyl-amino, mono-, di-, or tri-halopyrimidinylamino, 2,3- dihaloquinoxaline-6-carbonyl or -6-sulfonylamino, 1,4- dihalophthalizine-6-carbonyl or -6-sulfonylamino, 2- halobenzothiazole-4-carbonyl or -6-sulfonylamino, esterified sulfonic acid-oxalkylamide or oxaIkyl-sulfone groups, sulfofluoride, haloalkylamino, acryloylamino,

haloacylamino groups, and the like.

The new dyestuffs of the formula (XVIII) are obtained by forming such according to known methods through condensation and/or metallization and/or diazotization and coupling. This is accomplished by introducing into an amino group-containing dyestufi or dyestuff intermediate a pyrimidinylamino group having the formula N (lh) wherein Y, Z, and R have the above-indicated meanings via the nitrogen atom of the amino group which is bonded to a ring carbon atom of the aryl nucleus of the dyestuff or the dyestuff intermediate and transforming such where a dyestuff intermediate is employed into the desired end dyestuff. In order to introduce group (Ib) into amino group-containing dyestuff or dyestuff intermediates which contain a reactive hydrogen on the amino nitrogen, such dyestuff or dyestuff intermediates are condensed with compounds having the general formula wherein Q is a radical which can be split off as an anion and wherein R, Y, and Z have the above-indicated meanings. Of the reactive substituents O which can be split off as anionic radicals, chlorine, bromine, and sulfonyl substituents are preferred. Further suitable radicals which can be split off as anions are, for example, F,SO M (M being H or a metal cation), quarternary ammonium groups, alkylmercapto, alkoxy, or aryloxy groups.

Pyrimidine derivatives of the formula (XXII) which are suitable for the reaction are, for example, 2 methysulfonyl-4,5-dichloropyrimidine, 2- methylsulfonyl-4-chloro-5-bromo-pyrimidine, 2- methylsulfonyl-4-chloro-5-bromo-6-methylpyrimidine,

2,4-bis-methylsulfonyl-5-chloropyrimidine, 2,4-bismethylsulfonyl-S-chloro-6-methylpyrimidine, 2,4-bisphenylsulfonyl-S-chloro-6-methylpyrimdine, 2-

methylsulfonyl-4,5-dichloro-6- chloromethylpyrimidine, 2-methylsulfonyl-4,5- dichloro-o-carboxymethylpyrimidine, or 2- carboxymethylsulfonyl-4,5-dichloro-6-methylpyrimidine, as well as those cited on page 11 hereinabove. The reaction of the amino group-containing dyestuffs or dyestuff intermediates with the heterocyclic compounds of the formula (XXII) is carried out, depending on the type of starting compounds employed, in an organic, aqueous-organic, or aqueous medium at temperatures of -lO to +C, preferably in the presence of alkaline-condensing agents such as pyridine, aqueous alkali metal carbonate, or alkali metal hydroxide solution.

When dyestuff intermediates are used, the condensation products obtained are converted in known manner intothe desired end dyestuffs. This process is mainly of interest for the preparation of azo dyestuffs in that, for example, a diazo and/or coupling component exhibiting a reactive amino group is first condensed with the reactive component (XXII) and the resultant intermediate product is subsequently converted into an azo dyestuff by diazotization, and/or coupling and/or eondensation. This azo dyestuff can be subjected to further conversion reactions customary in azo dyestuffs, e.g.

Ell

acylation, condensation, reduction, and metallization. Also in the preparation of other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (XXII) can first be carried out with an intermediate product, e.g. with M-phenylenediamine or a M-phenylene-diaminesulfonic acid and the resultant reaction product subsequently further consensed, e.g. with bromoamino acid (l-amino-4-bromoanthraquinone-2-sulfonic acid) to form a reactive anthraquinone dyestuff, or with a cop peror nickel-phthalocyanine-sulfonic acid halide to form a reactive phthalocyanine dyestuff.

Another method of preparing the novel dyestuffs of formula (XVII) consists in that amino groupcontaining dyestuffs or, in particular, dyestuff intermediates which exhibit an exchangeable hydrogen atom at the amino group, are reacted with compounds of the general formula LT (XXIII) wherein Y, Z, and Q have the meanings indicated hereinabove and T is a radical which can be split off as an anion with the exception of a sulfonyl radical, while replacing one of the radicals O which can be split off as an anion, thereafter transforming the radical T in known manner into sulfonyl substituents -SO R and, if dyestuff intermediates are employed, transforming such into the desired end dyestuffs.

The exchange of one or more substituents T capable of being split off as an anion, e.g. of halogen atoms, for sulfonyl substituents can be effected, e.g. by reacting thecompounds with alkyl or arylsulfonates or, if T represents, for example, an alkylmercapto or arylmercapto group which can be split off as anion, by transforming the latter by means of suitable oxidizing agents such as hydrogen peroxide, hypohalides, or perrnanganates, into the corresponding sulfonyl radicals.

The dyestuffs obtainable by the various processes described above can be subjected, as has already been mentioned for some cases, to further reactions customary for dyestuffs, in that, for example, methallizable dyestuffs are treated with metal-yielding agents, especially chromium, cobalt, copper or nickel salts; dyestuffs containing reducible groups, especially nitro groups, are reduced; dyestuffs containing acylatable groups, especially acylatable amino groups are acylatcd; or dyestuffs are subsequently treated with sulfonating agents such as chlorosulfonic acid, thionylchloride, oleum or SO;, in chlorinated hydrocarbons, in order to introduce further sulfonic acid groups into the products. The latter mentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs.

Depending on the number of reactive HNR groups (R2=hydrogen or a substituent such as a lower alkyl group) in the dyestuff radical or dyestuff intermediates which are suitable for the conversion, one or more groups of the formula (lb) can be incorporated into the dyestuffs. In the majority of cases, the number m will not exceed 4, but dyestuffs with more than 4, e.g. up to 8 groupings of the formula (lb). especially those of higher molecular structure. can also be synthesized.

If the dyestuffs prepared according to the invention contain groups forming metal complexes, then they can be converted into their metal complex compounds by the action of metal-yielding agents, e.g. copper, nickel, chromium, or cobalt salts. They can also be subjected to other customary conversion reactions such as diazotization, coupling, acylation, and condensation.

The new dyestuffs are highly valuable products which are suitable for a great variety of applications. As water-soluble compounds they are of special interest for the dyeing of textile materials containing hydroxyl groups or nitrogen, particularly of textile materials of natural and regenerated cellulose, as well as of wool, silk, synthetic polyamide and polyurethane fibers. Due to the reactive sulfonyl substituent or substituents in the heterocyclic ring A, the products are especially suitable as reactive dyestufi's for the dyeing of cellulose materials according to the techniques recently disclosed for this purpose. The fastness properties obtained, particularly the fastness to wet processing, are excellent.

For the dyeing of cellulose, the dyestuffs are preferably used in an aqueous solution which can be mixed with compounds of alkaline reaction, such as alkali metal hydroxide or alkali metal carbonate, or with compounds convertible into substances of alkaline reaction, such as alkali metal bicarbonate. Further adjuvants can be added to the solution, but these must not react with the dyestuffs in an undesirable manner. Additives of this type are, for example, surface-active compounds such as alkyl-sulphates, or compounds pre venting migration of the dyestuff, or dyeing auxiliaries, such as urea (for improving the solubility and fixation of the dyestuffs), or inert thickeners, such as oil-inwater emulsions, tragacanth, starch alginate, or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be dyed, for example, by padding on the foulard (short bath) or by printing, and subsequently heated for some time at an elevated temperature, preferably at 40 to l50C. Heating can be carried out in the hot flue, in a steaming apparatus, on heated rolls, or by introduction into heated concentrated salt baths, using these methods in any desired sequence or any of them alone.

When a padding or dyeing liquor without alkali is used, the dry goods are subsequently passed through a solution of alkaline reaction to which sodium chloride or Glaubers salt is added. The addition of salt reduces the migration of the dyestuff from the fiber.

The material to be dyed can also be previously treated with one of the above-mentioncd acid-binding agents, subsequently treatcdwith a solution or paste of the dyestuff and finally fixed, as stated, at an elevated temperature.

For the dyeing from a long bath, the material is introduced into an aqueous solution of the dyestuff (liquor ratio 1:5 to 1:40) at room temperature and dyeing is carried out, possibly while raising the temperature to C, for 40 to minutes with the portionwise addition of salt, e.g. sodium sulphate, and subsequently of alkali, for example, sodium phosphates, sodium carbonate, or alkalis. The chemical reaction between the dyestuff and the fiber thereby occurs. After completion of the chemical fixation, the dyed material is rinsed hot and finally soaped, whereby non-fixed residues of the dyestuff are removed. Dyeings of excellent fastness, especially to wet processing and light, are thus obtained.

In the so-called cold batch -pad process, subsequent heatig can be dispensed with if the padded fabric is stored at room temperature for some time, e.g. for to 40 hours. A stronger alkali is used in this process than in the dyeing process from a long bath described above.

For printing materials containing hydroxyl groups, a printing paste is used which consists of the dyestuff solution, a thickener such as sodium alginate, and a compound of alkaline reaction or splitting off alkali upon heating, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate, or sodium and potassium bicarbonate, and the printed material is rinsed and soaped.

If the dyestuffs contain groups which form metal complexes, the fastness properties of the dyeings and prints can frequently be improved by an aftertreatment with metal-yielding agents, such as copper salts, e.g. copper sulphate, chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

Materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers are generally dyed by the dyeing methods customary for this purpose in the acidic to neutral range, and it is sometimes of advantage finally to raise the pH value of the dyebath, e.g. to pH 6.5 to pH 8.5.

The dyestuffs are applied, for example, to synthetic polyamide fibers in the form of solutions or, preferably, in a dispersed form and subsequently after-treated, possibly together with acid-binding agents, such as sodium carbonate (preferably in smaller amounts). Especially advantageous results are achieved with those dyestuffs which are insoluble or only hardly soluble in water. These are worked up by known methods and with the addition of the known adjuvants into a dyestuff dispersion and applied as such from a dyebath and/or padding liquor, or in a printing paste. Suitable adjuvants for this application are, inter alia, compounds which prevent the migration of the dyestuff on the fibers, such as cellulose ethers, alkali metal chlorides and sulphates, wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols, solvents, such as thiodiglycol, as well as thickening agents, such as starch, tragacanth, alginate thickening, gum arabic, etc.

The after-treatment of the dyeings, impregnations and prints obtained on fabrics of polyamide fibers is preferably carried out at a temperature of 50 to 1 10 C for a period of 5 to 60 minutes. Also in this case the fastness properties of the dyeings can sometimes be improved, provided the dyestuffs employed contain metal complex-forming groupings, by means of metalyielding agents, such as copper salts, e.g. copper sulphate, or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

In general, the dyeings which can be obtained with the new dyestuffs are characterized by good to very good fastness properties, especially by excellent fast ness to wet processing.

If compared with known reactive dyestuffs which contain 2,3-dichloroquinoxaline-6-carbonylamino or chloro-triazinylamino or chloro-pyrimidinylamino as the fiber-reactive groups, the novel dyestuffs of the present invention having, for instance, a 2- methylsulfonyLS-chloro-6-methylpyrimidinyl-4-amino fiber-reactive grouping are far superior in the fastness to washing (in the presence or absence of alkaline substances) and in the fastness to acids (organic and inorganic) of their dyeings on cellulose-containing textiles, such as cotton and regenerated cellulose. In comparison with chloro-triazinylamino and chloropyrimidinylamino fiber-reactive dyestuffs the dyestuffs of the present invention exhibit the further advantage that they can be (chemically) fixed when padded on cellulose containing textiles, such as cotton and regenerated cellulose, in much shorter times. Whereas known reactive dyes need about 5 to 8 minutes of heat treatment, the novel dyestuffss can be fixed within about 30 seconds to 1 minute (the fixation is reached by steaming at about 104 to 105 C or thermofixation at about C).

The novel dyestuffs of the present invention are more specifically distinguished from reactive dyestuffs of the prior art by the combination of the heterocyclic group and the reactive sulfonyl group. It is the combination of these chemical moieties which results in the superior properties described in the application. The term reactive sulfonyl substituent, as used herein, means that the sulfonyl substituent must be attached to a carbon atom of the heterocyclic ring which will not inactivate the sulfonyl group. Thus, sulfonyl substituents attached to the 5-position of the pyrimidinyl ring, such as described in the dyestuffs disclosed in British Pat. No. 822,948, do not react with the hydroxyl groups and similar reactive groups in the fiber compositions, and in the case of the pyrimdinyl group, it is essential that the sulfonyl substituent be located at the 2-, 4-, or 6- position in order for the dyestuffs to react with the fiber composition. Similarly, the properties of the dyestuffs of the present invention are not obtained if the reactive sulfonyl substituent is not attached to the described heterocyclic ring but is attached to, for example, an alkylene radical such as described, for example, in British Pat. No. 921,258. As compared to the dyestuffs of the present invention, the dyestuffs containing the combination of an aliphatic radical and a sulfonyl substituent are deficient in the fastness to hydrolysis in acid or alkaline medium of the fibre-dyestuff bond as well as in their reactivity in the coloring of cellulose-containing or amide group-containing textile materials.

The following examples are given for the purpose of illustrating the invention, the parts being parts by weight, unless otherwise stated.

EXAMPLE 1 To a solution of 34.7 parts of Z-aminonaphthalene- 4,8-disulfonic acid sodium salt and 7 parts of sodium nitrite in 300 parts of water are added 28 parts by volume of concentrated hydrochloric acid while cooling with ice, and the mixture is stirred at 0 to 10 C for 30 minutes. After removing the excess nitrous acid, 10.7 parts of 3-aminotoluene dissolved in 10 parts by volume of concentrated hydrochloric acid and 150, parts of water are added, and coupling is completed by neutralizing the mixture to pH 35. The resultant aminoazo dyestuff is salted out, filtered off with suction, washed and then redissolved at ph 7 in 700 parts of water with the addition of a sodium hydroxide solution. The aqueous solution is then mixed with 21 parts of 2- methylsulfonyl-4-chloro-6-methyl-pyrimidine and vigorously stirred. The temperature of the reaction mixture is maintained at about 65 c by heating; the liberis salted out with 80 parts of sodium chloride, pressed off, washed and dried at about 50 C in a vacuum. It is a yellow powder which dissolves in water, with a yellow color.

When a cellulose fabric is printed with a printing paste which contains, per kilogram, 15 g of the dye stuff, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g of sodium alginate per kg thickener), 2 g of sodium hydroxide and g of sodium carbonate, and which has been made up with water to l kilogram, the fabric is then dried, steamed at 105 C for 8 minutes, rinsed with hot water, and soaped at the boil, an intense, reddish-yellow print of good fastness to washing and light is obtained.

EXAMPLE 2 The copper complex compound is prepared according to the instructions of German Pa tent Specification No. 1,1 17,235 by coupling of diazotized 1-amino-8-( benzene-sulfonyloxy )-napthalenedisulfonic acid-(3,6) in a soda-alkaline medium with the equivalent amount of 2-aeetylamino-5- hydroxynapthalene-disulfonic acid-(4,8), conversion of the monoazo compound into the copper complex by oxidative coppering, and hydrolysis of the acetyl and benzene-sulfonyl group. This complex, 0.1 mol, is dissolved at pH 6-6.5 in 2500 parts by volume of water at 60 to 65 C and mixed at this temperature with 0.12 mol of 2,4-bis-methylsulfony1-6-methyl-pyrimidine.

A pH of 7-7.5 is maintained during the condensation by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out and isolated. When dried, the dyestuff is a dark powder which dissolves in water, with a blue color.

A cotton fabric, 100 parts, is treated on the foulard at room temperature with an aqueous solution containing 2% of the dyestuff, 15 g/liter of sodium bicarbonate and 150 g/liter of urea, subjected to intermediate dry ing, heated at 140 C for 10 minutes, then rinsed and soaped at the boil. The fabric is dyed in very clear blue shades fast to wet processing.

EXAMPLE 3 The monoazo dyestuff obtained following the procedure of Example 1 by coupling diazotized 2- arninonapthalene-4,8-disulfonic acid with 3- methylamino-toleune, 46 parts, is dissolved at pH 7-8 in 400 parts of water at to 6 5 C, the solution is mixed portionwise with a total of 25 parts of 2,4-bismethylsulfonyl d-methyl-pyrimidine in the presence of excess sodium acetate or calcium carbonate and stirred at the same temperature, until acidification of a sample no longer leads to a change of color. The resultant dyestuff, believed to have the formula is salted out, filtered off with suction, washed and dried.

A cotton fabric is impregnated with a solution at 20 to 25 C, which contains, per liter of liquor, 20 g of the above dyestuff and 0.5 g. of a non-ionic wetting agent (eg a polyoxethylated oleyl alcohol) as well as 150 g of urea and 15 g of sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about After an intermediate drying at 50 to 60 c, the fabric is heated at C for 10 minutes and the dyeing thus obtained is thoroughly rinsed with hot water and treated for 20 minutes at the boil with a solution containing, per liter, 5 g of Marseilles soap and 2 g of sodium carbonate. After rinsing and drying, an intense, reddish-yellow shade of good fastness to wet processing, rubbing, and light is obtained.

The following Table gives the diazo components, coupling, and the reactive components which can be linked to the amino group, from which dyestuffs can be synthesized in analogy with Examples l-3; the shades obtained by one of the methods of application described above are also specified in the Table.

Abbreviations for A: 2'mcthy1sulfonyl-4-ch1orw6- the reactive components: methyl-pyrimidine 2,4-bis-mcthy|sulfony1-6- methyl-pyrimidine Example Diazo Coupling Reactive Shade No. component component component 4 2-aminonaphthalene-4,8- l-amino-2-methoxy-5- A yellow disulfonic acid mcthylbenzene 5 do. do. B do. 6 l aminonaphthalene-3,6- l amino-B-meIhyIbenZene A do.

disulfonic acid 7 do. do. B do. 8 Q-aminonuphthalene-S,7- 1-amino-3-methylbenzenc A do.

disulfonic acid 9 do. do. B do. 10 2-aminonaphthalenc ofil-aminoJ-methylbenzcne A do.

disulfonic acid 1 I do. do. B do.

Continued Abbreviations for the reactive components:

Z-methylsulfonvl-4-chloro-6- methyl-pyrimidine 2,4-brs-mcthylsulfortylo methyl-pyrimidine Diazo component Coupling Example No. component 4-aminoazobenzene-3,4

disulfonic acid l aminobenzene-4-sulfonic lamino-3-methylbenzene Reactive Shade component A brownyellow B brownyellow A yellow B do.

A do.

A do.

The examples presented in the foregoing tubular form are repeated using instead of the 2-methylsulfonyl-4-chloro6methyl-pyrimidine, equivalent amounts of 2-methyl-sulfonyl-4,5-dichloro-6-methylpyrimidine and instead of the 2,4-bis-methyl-sulfonylo-methyl-pyrimidine, equivalent amounts of 2,4-bismethyl-sulfonyl-5-chloro-6-methyl-pyrimidine. The corresponding reactive dyestuffs containing the 5- chloro-pyrimidine groups are obtained and are employed with the same results in the described procedures.

EXAMPLE l8 sulfonic acid dissolved in 200 parts of water. The dye- 4 stuff of the formula formed at a final pH of about 7, is salted out with 100 parts of sodium chloride, filtered off with suction,

washed and dried at 30 to C in a vacuum. The dyestuff forms small red needles of metallic luster which readily dissolve in water, with a red color.

When a fabric of cotton or regenerated cellulose is dyed or printed with this dyestuff according to the process described in Example 1, clear bluish-red shades and prints of good fastness to wet processing, rubbing, and light are obtained.

Equally good results are obtained according to the following process.

Cotton skein, g, is dyed in 1 liter of a dyebath which contains 1.5 g of the above dyestuff, by raising the temperature within 30 minutes from 20 C to about 80 C while adding a total of 50 g of sodium chloride in several portions, subsequently adding 20 g of sodium carbonate and treating the material at this temperature for minutes. After rinsing, soaping at the boil, and drying, a bluish-red shade of good fastness to wet processing, rubbing, and light is obtained.

The foregoing example is repeated employing instead of the 2,4-bis-methyl-sulfonyl-6-methyl-pyrimidine, equivalent amounts of 2,4-bis-methyl-sulfonyl-5- chloro-o-methyl-pyrimidine. The corresponding reactive dyestuff containing the 5-chlor0-pyrimidine group 5 is obtained and is employed with the same results in the described procedures.

The following Table gives the shades of further dyestuffs which are synthesized from the diazo components, coupling components, and reactive components which can be linked to the amino group in the coupling component employing the procedure of Example 18, or also by reacting the corresponding aminoazo dyestuffs with the reactive components, and which can be applied to cellulose materials by dyeing or printing according to one of the processes described above.

The abbreviations for the reactive components A and B have been defined in Examples 4-! 7.

Example Diazo Coupling Reactive Shade No. Component component component 19 l-aminobcnzene-Z- l-amino-8-h droxy- B red sulfonic acid napthalenc- ,6- disulfonic acid 20 aminobenzcne l-( 3 '-aminobenzyl- A do.

amino )-8-hydroxynupthalene-lodisulfonic acid 2 1 do. do. B do.

- Continued Example Diazo Coupling Reactive Shade No. Component component component 22 l-amino-2-carboxybenzcnel-amino-S-h droxy- A do.

4-sulfonic acid napthalcnc-fi bdisulfonic acid 23 l-amino-4-methylbenzenedo. do.

l-sulfonic acid 24 l-amino-3l-amino3-acetylamino do. B do.

benzcnc--sulfonic acid 25 l-amino-3-( 2 -[4- do. do,

sulfophen lamino]-4'-chlorotriazine-l ,3',5"yl-6)- aminobenzcnc-o-sulfonic acid 26 l-aminobcnzenc-Z-sulfonic Z-amino-S-hydroxy- A orange acid napthalene-7- sulfonic acid 26a l-amino-3-( 2 4 '-sulfo- 2-amino5-hydroxy- A do.

phcnylamino1-4methylaminonaphthalene-7- triazinc-l,3.5-y|-6)' sulfonic acid aminobenzene-o-sulfonic acid 27 I-timinobcnZcne-Z- Z-methylamino-S- A orange sulfonic acid hydroxy-napthalene- 7-sulfonic acid 28 l-amino-4-acetyl do. A scarlet amino-6sulfonic acid 29 do. 2-arnino-5hydroxy- A do.

na hthalene-7- su fonic acid The examples presented in the foregoing tabular 25 sotNa NI-I oo o.,it5

form are repeated using instead of the 2-methyl sulfonyl-4-chloro-6-methyl-pyrimidine, equivalent amounts of Z-methyl-sulfonyl-4,5-dichloro-6-methyl pyrimidine, and instead of the 2,4-bis-methyl-sulfonyl- -methyl-pryimidine, equivalent amounts of 2,4-bismethyl-sulfonyl-S-chloro-o-methyl-pyrimidine. The corresponding reactive dyestuffs containing the 5- chloro-pyrimidine group are obtained and are employed with the same results in the described procedures.

EXAMPLE 30 Into a solution of 21 parts of the sodium salt of l,S-diaminobenzene-6-sulfonic acid in 100 parts of water are introduced, with good stirring, 25.0 parts of 2-methylsulfonyl-4-chloro--methyl-pyrimidine and the mixture is stirred at 60 to 65 C, while continuously neutralizing the liberated hydrochloric acid to pH 7-8, until diazotization of a sample and coupling with l-hydroxynapthalene-4-sulfonic acid yields a clear yellowish-red coloration. After the addition of ice, the resultant dyestuff intermediate is directly diazotized with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and the product is subsequently added to a solution of 47 parts of the sodium salt of lbenzoylamino-8-hydroxy-naphthalene-3,6-disulfonic acid and 12 parts of sodium carbonate in 200 parts of water, whereupon coupling takes place, giving the dyestuff of the formula which is salted out, filtered off with suction, washed and dried at 30 to 40 C in a vacuum. The dyestuff readily dissolves in water, with a red color, and yields clear bluish-red shades, and prints on cellulose materials by one of the processes described above.

The foregoing example is repeated employing instead of the Z-methyl sulfonyl-4-chloro-6-methyl-pyrimidine, equivalent amounts of 2-methyl sulfonyl-4,5-chloro6- methyl-pyrimidine. The corresponding reactive dyestuff containing the 5-chloro-pyrirnidine group is obtained and is employed with the same results in the described procedures.

The following Table gives the shades and the pH value of the coupling medium of dyestuffs which are prepared by following the procedure of Example 30 from a diazo component containing a further, preferably acylatable, amino group, a coupling component and a reactive component which can be linked to the diazo component. The processes described above can be used for dyeing and printing of cellulose materials with the dyestuffs of the Table below.

Abbreviations for the reactive components A and B have been defined in Examples 4l 7.

Example Diazo Coupling Reactive pH of Shade No. component Component component coupling medium 3 l l.3-diaminobenzenc- Z-aminonaphthalene- A 4-5 orange 4-sulfonic acid 5,7'disulfonic acid 32 do. 2-aminonaphthalene- A 4-5 do.

3,6-disulfonic acid 33 do. Z-aminonaphthalene- B 4-5 do.

o-sulfonic acid 34 do. Z-N-methylamino-S- A 4-5 do,

hydroxynaphthalcneo-sulfonic acid 35 do. l-( 3,5'-dichloro-l A 744 red 2. '-thiazole-4 '-carbonamido )-8-hydroxynaphthalcnc-3,6-disulfonic acid Continued Example Diazo Coupling Reactive pH of Shade No. component Component component coupling medium 36 1,3-diaminobenzenel-(2,4'-dihydroxy B 7-8 red 4-sulfonic acid triazine-l .3.5',-yl-

6'-amino)-8-hydroxy naphthalenelodisulfonic acid 37 do. l(3',5'dichloro-l A 7-8 do.

2'-thiazole-4'-carbon amido)-8-hydroxynaphthalene-3,6-disulfomc acid 38 do. Z-hydrox naphthalene- A 8 scarlet 3,6-disul onic acid 39 do. l-acetylamino-8-hydroxy- B 7-8 red naphthalene-3,6- disulfonic acid 40 do. l-(3'-sulfophenyl)-3- A 6 yellow methyl-pyrazolone-S 4 l do. l-( 2',5 '-dichloro-4- A 6 yellow sulfophenyl )-3-methylpyrazolone-S 42 do. l-(,7'-disulfonaph- A 6 yellow thyl-2-)-3-methylpyrazolone-S 43 do. l-(3'-sulfophenyl)-3- B 6 do.

methyl-S-aminopyrazole 44 1,4-diaminobenzene- 2-amino-8-hydroxynaphtha- A 44.5 red 3-sulfonic acid lene-o-sulfonic acid 45 do. Z-acetylaminoS-hydroxy- A 67 scarlet naphthalene-'l-sulfonic acid 46 do. l-acetylamino5-h droxy- B 67 red naphthalene-7-sul onic acid The examples presented in the foregoing tabular form are repeated using instead of the 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine, equivalent amounts of 2-methyl-sulfonyl-4,5-dichloro-6-methylpyrimidine and, instead of the 2,4-bis-methyl-sulfonyl- 6-methyl-pyrimidine, equivalent amounts of 2,4-bismethyl-sulfonyl-5-chloro-o-methyl-pyrimidine. The corresponding reactive dyestuffs containing the 5- chloropyrimidine group are obtained and are employed with the same results in the described procedures.

EXAMPLE 47 The dyestufi of the formula l SOaNa,

amino groups can no longer be detected, the resultant reactive dyestuff of the formula is salted out, pressed off, washed and dried in a vacuum at 30 to 40C. Fabrics of cellulose materials can be dyed or printed with this dyestuff by one of the processes described above, in ruby shades fast to wet processing, rubbing, and light.

The foregoing example is repeated employing instead of the 2-methyl-sulfonyl-4-chloro-6-methyl-pyrimidine, equivalent amounts of 2-methyl-sulfonyl-4,S-dichloro-o-methylpyrimidine. The corresponding reactive dyestuff containing the 5- chloro-pyrimidine group is obtained and is employed with the same results in the described procedures.

The following Table gives the heavy metal complexes of further aminoazo dyestuffs and the reactive components linked to the amino group, as well as the shades of these dyestuffs on cellulose materials. The preparation of the amino dyestuffs and of their metal complexes, and the reaction of the latter with the reactive components can be carried out according to the procedures of Example 47.

Reactive components A and B are defined as in Examples 4-17.

Example Amino-azo (shown in terms of Complex Reactive Shade No. dyestuff components coupled) linked component heavy metal 48 l-hydroxy-2-aminobenzene-4,6- Cu A ruby disulfonic acid 2-amino-5-hydroxynaphthalene-7-sulfonic acid 49 l-hydroxy-2-uminobenzenc-4- Cu A ruby sulfonic acid 2-ethylamino-5-hydroxynaphthaleneJ-sulfomc acid 50 l-amino-Z-h droxy-6-nitro-naphthalcne-4- Cu A ruby sulfonic aci 2 amino-5-hydroxynaphthaleneJ-sulfonic acid do. Cr A grrcenish c 52 l-amino-2-hvdroxy-6-nitronaphthlene-4- Co ddi h suli'onic aci Lamino-S-hydroxyhlnck naphthalene-4-sulfonic acid H l-amino-Z-h 'droxy-5-mcthylsulfon l- Cu A klCl benzene -amino X-hydroxynaphthalene-3,fi-disulfonic acid 54 do. Co A grey 55 do. Cr A greenish black 56 l-amino-2-mcthy|henzenc-4-sulfonic Cu blue acid 1 -amino Z-hydroxy-S-methylbenzene 1 -amino-8-hydroxy naphthalene-4,6- disulfonic acid 5 7 l-amino 2-methylbenzene-4-sulfonic Co B grey acid l-amino 2-hydroxy-S-mcthylbenzene l-amino8hydroxynaphthalene-4.6- disulfonic acid 58 do. Cr A greenish black 59 l-amino-2-chlorobcnzene-4 sulfonic acid Cu A navy blue l-hydroxy-2 acetylaminobenzene), hydrolysed, l amino-8hydroxy-naphthalene- 3,6-disulfonic acid 60 do. Co A grey 6 l l-amino8hydroxynaphthalene-4-sulfonic Co A black acid -l-hydrox -2,6-diaminobenzene-4- sulfonic acid- ,3-dihydroxybenzene 62 l-amino-8hydroxynaphthalene-3 .G-disulfonic Co A do.

acid l-hydroxy-2,6-diaminobenzene-4 sulfonic acid -2-hydroxy-naphthalene 63 l'amino-S-hydroxynaphthalene-4-sulfonic Co A do.

acid l-hydrox -2,6-diaminobenzenc-4- sulfonic acid -methyl-pyrazolone-(5) The examples presented in the foregoing tabular form are repeated using instead of the 2-methylsulfonyl-4-chloro-6-methylpyrimidine, equivalent amounts of 2-methyl-sulfonyl-4,5-dichloro-6-methylpyrimidine and, instead of the 2,4-bis-methyl-sulfonyl- 6-methyl-pyrimidine, equivalent amounts of 2,4-bismethyl-sulfonyl-5-chloro-6-methyl-pyrimidine. The corresponding reactive dyestuffs containing the 5- chloropyrimidine group are obtained and are employed with the same results in the described procedures.

EXAMPLE 64 The copper-phthalocyanine tetrasulfochloride freshly prepared in the usual manner by the reaction of chlorosulfonic acid and thionyl chloride with copperphthalocyanine, or of the isomeric copperphthalocyanine tetrasulfochloride synthesized from 1- sulfobenzene-3,4-dicarboxylic acid via the corresponding copper-phthalocyanine tetrasulfonic acid, 96 parts Cu- P hthaloeyanine l (referred to 100% goods), are suspended in the form of the moist, thoroughly washed filter cake in 500 parts of water and 500 parts of ice, a solution of 50 parts of the sodium salt of l,3-diaminobenzene-4-sulfonic acid in 500 parts of water, is added and the pH is adjusted to 8.5 with sodium carbonate. The suspension is stirred at room temperature for 24 hours, while maintaining a constant pH of 8.5 by the continuous addition of sodium carbonate. The resultant condensation product is precipitated at pH l-2 by the addition of sodium chloride, filtered off with suction, washed, and then redissolved neutral in 1000 parts of water. 71 Parts of 2,4- bis-methyl-sulfonyl-6-methyl-pyrimidine are introduced into the blue solution with intense stirring, and the reaction mixture is stirred at 60 to C while continuously neutralizing it to pH 7-8 by means of a sodium carbonate solution, until free amino groups can no longer be detected. The reactive dyestuff of the formula l solcm N NH N i l thus obtained is salted out, washed and dried at 30 to 40C in a vacuum. It is a dark blue powder which dissolves in water, with a blue color, and dyes cotton and regenerated cellulose by one of the dyeing or printing processes described above in clear blue shades of good fastness to wet processing,- rubbing, and light.

Instead of 96 parts of copper-phthalocyanine tetrasulfochloride, there can also be used 87 parts (referred to 100% goods) of the copperor nickelphthalocyanine trisulfochloride obtainable by the reaction of chlorosulfonic acid with copperor nickelphthalocyanine, in the form of the moist filter cake thoroughly washed with ice water, the procedure being otherwise the same as in Example 64; reactive dyestuffs yielding clear blue shades are thus likewise obtained.

When the proceduree described in Example 64 is followed, except employing 87 parts of copperphthalocyanine tri-sulfochloride and using 90 parts of the sodium salt of 4,4'-diaminodiphenyl-2,2-disulfonic acid or 90 parts of the sodium salt of 4,4"-diaminostilbene-2,2'-disulfonic acid, instead of 50 parts of the sodium salt of l,3-diaminobenzene-4-su1fonic acid, reactive dyestuffs are again obtained which dye cellulose materials by one of the processes described above in clear blue shades fast to wet processing, rubbing, and light.

When 4 ,4 ,4 4' '-tetraphenyl-Cuphthalocyanine is used as starting material, sulfochlorination and reaction with 1,3-phenylene-diamine- 4-sulfonic acid, followed by acylation with 2,4-bismethyl-sulfonyl-6-methy1-pyrimidine yield a reactive dyestuff which dyes cellulose materials in the presence of acid-binding agents in clear green shades fast to wet processing and light.

The foregoing example is repeated employing instead of the 2,4-bis-methyl-sulfony1-6-methy1-pyrimidine, equivalent amounts of 2,4-bis-methyl-sulfonyl-5- chloro-6-methyl-pyrimidine. The corresponding reactive dyestuff containing the 5-chlor0-pyrimidine group is obtained and is employed with the same results in the described procedures.

EXAMPLE 65 The amino-anthraquinone dyestuff obtained by reacting -amino-4-bromo-anthraquinone-2-sulfonic acid with an excess of 4,4-diamino-diphenyl-2,2'- disulfonic acid, 71 parts, is dissolved in 700 parts of water; parts of 2-methyl-sulfonyl-4-chloro-6-methyl pyrimidine are added at 60 to 65C with good stirring, and a pH of 77.5 is maintained by the continuous addition of a sodium carbonate solution. When amino groups can no longer be detected, the resultant dyestuff of the formula is salted out, filtered off with suction, washed and dried at to 40C in a vacuum. The dyestuff dyes cotton and regenerated cellulose by one of the processes described above in blue shades fast to wet processing, rubbing, and light.

Following the procedure of Example 65 but using instead of the 71 parts of the starting dycstuff there employed, equivalent amounts of one of the following derivatives of 1-amino-4-( aminoarylamino anthraquinone-Z-sulfonic acid, similar dyestuffs are obtained, which likewise yield blue shades with fastness properties similar to those of the dyestuff obtained above: 1 -amino-4-( 4-amino-2 '-su1fophcny1amino)- anthraquinone-2-sulfonic acid, 1-amino4-(4 aminophenylamino)-anthraquinone-2,6-disu1fonic acid, isomer mixture of l-amino-4-( 4- aminophenylamino)-anthraquinone-2,5- and -2,8- disulfonic acid, isomer mixture of l-amino-4-(4'- amino-2'-sulfophenylamino)-anthraquinone-2,5- and -2,8-disu1fonic acid, isomer mixture of 1-amino-4-(3- aminophenylamino)-anthraquinone-2,5- and -2,8- disulfonic acid, 1-amino-4-( 3 '-aminophenylamino anthraquinone-2,6-disulfonic acid, l-amino-4-( 3 amino-4-sulfopheny1amino)-anthraquinone-2-sulfonic acid. With l-arnino-4-(4-[4-amino2' sulfophenyl1aminophenyl)-anthraquinone-2,6- disulfonic acid there are obtained reactive dyestuffs which dye in bluish-grey shades.

The foregoing example is repeated employing instead of the Z-methyl-sulfonyl-4-chloro-6-methyl-pyrimidine, equivalent amounts of 2-methyl-sulfonyl-4,5-dichloro- 6-methy1-pyrimidine. The corresponding reactive dyestuff containing the 5-chloropyrimidine group is obtained and is employed with the same results in the described procedures.

EXAMPLE 66 Employing the procedure of Example 47, but using instead of the copper-containing amino-monoazo dyestuff there employed, the equivalent amount of the chromium complex of the aminoazo dyestuff obtained by coupling diazotized l-amino-2-hydroxy-3- chlorobenzene-S-sulfonic acid with 1-[3'-(3"- aminophenyl)]-sulfony1imido-sulfophenyl-3-methylpyrazolone-(S), a reactive dyestuff is obtained which dyes cellulose materials by one of the processes described above in yellow-brown shades of good fastness to wet processing, rubbing, and light.

The foregoing example is repeated employing instead of the 2-methyl-sulfonyl-4-chloro-6-methy1-pyrimidine, equivalent amounts of 2-methyl-sulfony1-4,5-dichloro- 6-methylpyrimidine. The corresponding reactive dyestuff containing the 5-chloro-pyrimidine group is obtained and is employed with the same results in the described procedures.

EXAMPLE 67 In 3000 parts by volume of water is dissolved at a pH 6, 0.1 mol of the copper complex compound of the formula and the solution is combined at a temperature of about C, while stirring, with 21 parts (0.1 mol) of 2- methyl-sulfonyl-4-chloro-6-methyl-pyrimidine. The mixture is stirred, until the condensation is completed,

the dyestufi is separated by the addition of a little so dium chloride, and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained which dissolves in water, with a green color, and dyes cotton by the methods described in Examples 1-3, in green shades.

A cotton fabric is impregnated with a solution at 20 to 25C which contains, per liter of liquor, 25 g of the above dyestuff and 0.5 g of a non-ionic wetting agent (e.g. a polyoxethylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100%. After an intermediate drying at 50 to 60C, the fabric is heated at 140C for minutes, the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 20 minutes with a solution containing, per liter, 5 g of Marseilles soap and 2 g of sodium carbonate. After rinsing and drying, a green shade of good fastness to wet processing, rubbing, and light is obtained.

Clear green shades of good fastness properties are also obtained on cellulose materials by one of the other dyeing or printing processes described in Examples 1-3, 18, and 20.

The foregoing example is repeated employing instead of the Z-methyl-sulfonyl-4-chloro-6-methyl-pyrirnidine, equivalent amounts of 2-methyl-sulfonyl-4,S-dichloro- 6-methyl-pyrimidine. The corresponding reactive dyestuff containing the 5-chloropyrimidine group is obtained and is employed with the same results in the described procedures.

EXAMPLE 68 The paste of the aminoazo compound of the formula Sthll H0111 0.1 mol, which is obtained by coupling the diazonium compound from 6-acetamino-2-aminonaphthalene- 4,8-disulfonic acid with 2-hydroxynaphthalene-3,6- disulfonic acid, hydrolysis and conversion of the mono azo compound into the copper complex, is dissolved at pH 6.5 in 2000 parts by volume of water and combined with 25 parts of 2,4-bis-methyl-sulfonyl-6- methylpyrimidine. The reaction mixture is stirred at 60 to 65C, until the condensation is completed, while maintaining the pH of the reaction solution at 7-7.5 by the addition of sodium carbonate. When the reaction is completed, the dyestuff is salted out, isolated and dried in a vacuum.

The dry dyestuff is a dark powder which dissolves in water, with a violet color, and dyes cotton in the presence of alkali in bluish-violet shades.

The foregoing example is repeated employing instead of the 2,4-bis-methyl-sulfonyl-6-methyl-pyrimidine, equivalent amounts of 2,4-bis-methyl-sulfonyl-5- chloro-6-methyl pyrimidine. The corresponding reactive dyestuff containing the 5chloro-pyrimidine group is obtained and is employed with the same results in the described procedures.

EXAMPLE 69 An aqueous solution of 0.1 mol of the copper complex of the formula prepared according to the instructions of German Patent Specification No. 1,061,460 or 1,085,988, is reacted in the usual manner with 22 parts of 2-methylsulfonyl-4-chloro-6methylpyrimidine. A pH of 77.5 is maintained by the addition of sodium carbonate, and when the reaction is completed, the dyestuff is isolated by salting out. In the dry state, the dyestuff is a dark powder which dissolves in water, with a violet color. Cotton fabrics are dyed in violet shades fast to light and to wet processing.

The foregoing example is repeated employing instead of the 2-methyl-sulfonyl-4-chloro-6-methyl-pyrimidine, equivalent amounts of 2-methyl-sulfonyl-4,5-dichloro- 6-methyl-pyrimidine. The corresponding reactive dyestuff containing the 5-chloropyrimidine group is obtained and is employed with the same results in the described procedures.

EXAMPLE In 150 parts of water are dissolved 27.5 parts of 2- methylamino-5-hydroxynaphthalene-7-sulfonic acid sodium salt, the solution is mixed with 25 parts of 2,4 bis-methylsulfonyl-6methyl-pyrimidine and stirred at 50 to 55C, while continuously neutralizing the methane-sulfinic acid formed with a total of 34 parts by volume of a 16% sodium carbonate solution. The acylation is completed after a short time; the pH is 6 and changes no more.

Sodium bicarbonate. 30 parts. is then added and the diazo suspension prepared from 34 parts of the disodium salt of 2-aminonaphthalenel ,7-disulfonic acid in 200 parts of water is added dropwise at 20C within 15 minutes. The orange-colored reactive dyestuff of the formula S ouNzl S OzCIl'a CIT:

which is immediately formed, is completely separated, after further stirring for one hour, by the addition of parts of sodium chloride, filtered off, washed with a di lute sodium chloride solution, and. dried at 35C in a vacuum. The dyestuff dyes cellulose materials by the processes described above in reddish-orange shades of very good fastness to wet processing and good fastness to chlorine.

When equivalent amounts of 2-methyl-sulfonyl-4,5- dichloro-6methyl-pyrimidine are used in this example instead of 25 parts of 2,4-bis-methyl-sulfonyl-6-methylpyrimidine, a reactive dyestuff is obtained which dyes in orange shades and whose dyeing properties correspond to those of the reaction product of the bis-methyl-sulfonyl derivative.

Orange to red reactive dyestuffs are obtained in an analogous manner by acylating the aminonaphtholsulfonic acids listed in Column 3 of the following Table with 2,4-bis-methyl-sulfonyl-5-chloro-6-methylpyrimidine, or 2-methylsulfonyl-4,5-dichloro-6-methyl- 

1. A REACTIVE DYESTUFF OF THE FORMULA
 2. The reactive dyestuff of claim 1 in which F is the radical of water-soluble sulfo group-containing dyestuff in which
 3. The reactive dyestuff of claim 1 in which F is the radical of an organic dyestuff selected from the group consisting of azo, anthraquinone and azaporphin dyestuffs, in which
 4. A reactive dyestuff of the formula
 5. The reactive dyestuff of claim 4 in which F is the radical of a water-soluble sulfo group-containing azo dyestuff in which
 6. The reactive dyestuffs of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- is one of the following radicals wherein g is 0 to 2, h is 0 to 1, and k is 2 to 3:
 7. The reactive dyestuff of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- has the formula:
 8. The reactive dyestuff of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- has one of the following formulas wherein R'''' is hydrogen or hydroxyl, R''''1 is hydrogen, chlorine, methyl, or nitro, e is 1 to 2, g is 0 to 2, h is 0 to 1, k is 2 to 3, and Me is chromium or cobalt:
 9. The reactive dyestuffs of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- is one of the following radicals:
 10. The reactive dyestuffs of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- is one of the following radicals:
 11. The reactive dyestuff of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, y'' is methyl, and F- is one of the following radicals:
 12. The reactive dyestuff of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- is one of the following radicals:
 13. The reactive dyestuff of claim 4 wherein R''1 is hydrogen, R'' is methyl, Z'' is chlorine, Y'' is methyl, and F- is one of the following radicals:
 14. A compound of claim 12 having the formula 